EP2324118B1 - Verfahren zur Phosphorgewinnung aus Feststoffen unter Verwendung laugungsaktiver und phosphatakkumulierender Mikroorganismen - Google Patents

Verfahren zur Phosphorgewinnung aus Feststoffen unter Verwendung laugungsaktiver und phosphatakkumulierender Mikroorganismen Download PDF

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Publication number
EP2324118B1
EP2324118B1 EP20090781863 EP09781863A EP2324118B1 EP 2324118 B1 EP2324118 B1 EP 2324118B1 EP 20090781863 EP20090781863 EP 20090781863 EP 09781863 A EP09781863 A EP 09781863A EP 2324118 B1 EP2324118 B1 EP 2324118B1
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Prior art keywords
microorganisms
phosphorus
polyphosphate
phosphate
leaching
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EP20090781863
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German (de)
English (en)
French (fr)
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EP2324118A2 (de
Inventor
Jennifer Zimmermann
Wolfgang Dott
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Georg Fritzmeier GmbH and Co KG
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Georg Fritzmeier GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P39/00—Processes involving microorganisms of different genera in the same process, simultaneously
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
    • C05B13/06—Alkali and alkaline earth meta- or polyphosphate fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B15/00—Organic phosphatic fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P9/00—Preparation of organic compounds containing a metal or atom other than H, N, C, O, S or halogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/906—Phosphorus containing

Definitions

  • the invention relates to a process for selective phosphorus recovery from heavy metal and phosphate-containing solid material.
  • Phosphorus is a limiting nutrient for the growth of plants and, as it occurs exclusively in bound form, is degraded as phosphate ore in deposits that are finite in the form we know today. Mining phosphates are mainly processed into plant-available mineral fertilizer.
  • sewage sludge In the treatment of domestic or industrial wastewater, sewage sludge accumulates, which can be utilized agriculturally due to the nutrients nitrogen and phosphorus it contains.
  • pollutants such as heavy metals, such as lead and cadmium
  • agricultural sewage sludge utilization is increasingly called into question. Therefore, attempts are made to liberate the phosphate contained in the sewage sludge by targeted recovery as much as possible from heavy metals.
  • Phosphorus is removed or eliminated from sewage only in undissolved form, whereby biological and chemical-physical processes can be distinguished.
  • precipitation of the dissolved phosphate takes place by addition of precipitants.
  • the precipitants mainly Fe3 + , Al 3+ , Fe 2+ and Ca 2+ are used.
  • a disadvantage, however, is that the precipitants are partly by-products or waste products of large-scale processes and therefore contain impurities, such as heavy metals and organic halogen compounds, which increases the pollutant load of the sewage sludge.
  • iron phosphates can not be absorbed by plants. The use of pure precipitant is expensive.
  • phosphorus-containing solids such as sewage sludge ash
  • phosphorus is at least partially present in chemically bound form.
  • phosphorus remains completely as residue in the ash.
  • heavy metals such as Pb, Cd, Cu, Cr, Hg, Ni and Zn are usually present only as trace components in the ash, it may still exceed the limits set in the Fertilizer Ordinance. This requires further treatment of the ash.
  • the availability of phosphorus which is mainly present in the ash as apatite, is not sufficient for a nutrient supply of the plants without further treatment.
  • the document FR 2 595 687 A1 discloses a process for releasing phosphate from phosphate-containing solids, which comprises treating the phosphate-containing solid with leaching-active microorganisms under acidic conditions to liberate the phosphate from the solid, the liberated phosphate being used to produce a phosphate phosphorus-enriched plant-available nutrient source.
  • the object of the present invention was therefore to provide a simple and cost-effective process for obtaining phosphorus from heavy metal and phosphate-containing solids, in which the phosphorus can be isolated free of heavy metals. It has now been found that phosphorus can be efficiently released from such solids and separated from heavy metals when the solids undergo simultaneous treatment with leaching, aerobic sulfur-oxidizing microorganisms and polyphosphate-spanning microorganisms.
  • polyphosphate-storing microorganisms also bioaccumulate under the acidic conditions under which leaching of heavy metals and phosphate takes place of phosphate are able. In this way, the phosphorus in the form of biomass can be separated from unwanted heavy metals and be used for further use.
  • Leaching active microorganisms such as may be used in the present invention are aerobic sulfur oxidizing microorganisms, for example, sulfur oxidizing bacteria and archaea, as used in known conventional biological leaching processes ("bioleaching") to recover heavy metals from ores. These microorganisms are capable of dissolving heavy metal sulfides by oxidizing sulfides and elemental sulfur to sulfate to form sulfuric acid.
  • Microorganisms suitable for leaching include, but are not limited to, microorganisms of the genera Acidithiobacillus, Leptospirillum, Sulfobacillus, Acidimicrobium, Ferroplasma, Sulfolobus, Acidianus, Metallophaerea, Fulvimonas, Rhodanobacter, Alicyclobacillus, Dyella, Dokdonella and Acidiphilium.
  • Examples are microorganisms of the species Acidithiobacillus thiooxidans, Acidithiobacillus ferrooxidans, Acidithiobacillus caldus, Acidithiobacillus albertensis, Leptospirillum ferrooxidans, Leptospirillum ferriphilum, Fulvimonas soli, Rhodanobacter thiooxydans, Alicyclobacillus ferrooxydans, Dyella yeojuensis, Dokdonella koreensis and Acidiphilum cryptum.
  • Acidithiobacillus species such as Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans are particularly preferred leaching active microorganisms.
  • Polyphosphate-storing microorganisms for example polyphosphate-storing bacteria (also known as Bio-P bacteria), are aerobic microorganisms that take up more phosphorus than usual and store it in the cell.
  • phosphate-fixing and polyphosphate-storing bacteria are found, for example, in sewage treatment plants, for example in the Bio-P basin and in anaerobically stabilized sewage sludge (digested sludge), a mixture of about 95 to 99% water and 5 to 1% solids. If anaerobic / anoxic conditions occur in the activated sludge of a Bio-P basin or in a digester, numerous aerobic microorganisms are no longer able to absorb nutrients.
  • Polyphosphate-storing microorganisms use the energy from the stored polyphosphates to release phosphate under these stress conditions Nutrient absorption. If the bacteria then again oxygen available, the bacteria fill their energy storage in the form of polyphosphate again. It absorbs more phosphate than previously released.
  • Phosphate-storing microorganisms in a state after anaerobic stress conditions that replenish their phosphate storage under aerobic conditions are also referred to below as "anaerobically conditioned" polyphosphate-storing microorganisms. "Anaerobically conditioned" microorganisms are preferred.
  • Exemplary polyphosphate-storing microorganisms that can be used in the method of the present invention include, but are not limited to, microorganisms of the genera Pseudomonas, Aeromonas, Rhodocyclus, Tetrasphera and Acinetobacter.
  • leaching-active aerobic sulfur-oxidizing microorganisms and polyphosphate-storing microorganisms are used together as leaching liquor, the phosphate liberated under the acidic conditions of the process being accumulated by the phosphate-fixing and polyphosphate-storing microorganisms.
  • the microorganisms can come from individual cultures or, for example, from soil samples or sludges. They may be grown alone or together in suitable media, in the case of the polyphosphate-storing microorganisms, optionally exposed to anaerobic stress to degrade the phosphate stores, and then used in admixture under acidic conditions in the process of the invention.
  • the microorganisms used in the process according to the invention contain various types of leaching-active and polyphosphate-storing microorganisms.
  • the mixture used according to the invention may therefore also contain other aerobic and anaerobic microorganisms.
  • the mixture of microorganisms used in the method according to the invention is preferably obtained by enriching leaching-active sulfur-oxidizing microorganisms in an aqueous starting material which contains anaerobically conditioned polyphosphate-storing microorganisms.
  • starting materials containing polyphosphate-storing microorganisms are anaerobically stabilized sewage sludge or material as found in the anaerobic stage of a Bio-P basin. Anaerobically stabilized sewage sludge is preferred as the starting material.
  • the enrichment of the sulfur-oxidizing microorganisms is advantageously carried out by such a starting material which usually contains as endogenous microorganisms and sulfur-oxidizing microorganisms, in particular Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans, with the addition of an oxidizable sulfur source, for example in the form of elemental sulfur or sulfides, preferably together with iron sulfate (FeS04), cultured under aerobic conditions.
  • Sulfur oxidizing microorganisms use CO 2 as a carbon source and grow preferentially under these conditions.
  • desired sulfur-oxidizing microorganisms can also be added to the starting material, which are then enriched.
  • the cultivation is preferably carried out at a temperature between 15 and 37 ° C, preferably between 20 and 30 ° C. Since sulfur-oxidizing microorganisms such as Acidithiobacillus thiooxidans produce this in large quantities sulfuric acid, the pH of the starting material, which is usually between 7 and 8, can fall to less than 2. It has surprisingly been found that the polyphosphate-storing microorganisms tolerate cultivation under these acidic conditions.
  • the cultivation is continued until the pH has reached the desired value, advantageously a pH of 4.0 or lower, more preferably between 1.0 and 3.5, for example between 1.5 and 3.5 or 2 , 0 and 3.5, and most preferably between 1.5 and 2.5, for example between 2.2 and 2.5. Thereafter, the solid particles are preferably separated.
  • the culture liquid obtained in the culture containing the sulfur-oxidizing and polyphosphate-storing microorganisms can be used as the leaching liquid in the process of the present invention. Accordingly, such a leaching liquid may also contain other aerobic or anaerobic microorganisms present in the starting material.
  • the microbial composition obtained in this way and containing enriched leaching-active, aerobic sulfur-oxidizing and anaerobically conditioned polyphosphate-storing microorganisms is likewise provided by the invention.
  • Solids which can be treated by the process of the invention for the production of phosphate are leachable heavy metal and phosphate-containing solids. Such solids may be naturally occurring or obtained after heat treatment or dehydration.
  • solids which can be advantageously treated by the process of the present invention are incineration ashes such as sewage sludge ash, animal and bone meal, industrial slag, soil, sludge, landfill soils and manure.
  • the leaching-active microorganisms oxidize the heavy metal sulfides and thus bring the metals into solution.
  • chemically bound phosphorus is digested under these acid leaching conditions and also brought into solution. If the sulfur content of the treated solids is very low, the treatment can also be carried out with the addition of oxidizable sulfur, for example in the form of elemental sulfur or sulfides.
  • the inventive method is usually at a pH of ⁇ 4.0, more preferably between 1.0 and 3.5, for example between 1.5 and 3.5 or 2.0 and 3.5, and most preferably between 1 , 5 and 2.5, for example between 2.2 and 2.5.
  • the optimum pH can be determined by the skilled person by simple experiments and optionally kept stable.
  • the inventive method is usually carried out at a temperature between 15 and 30 ° C and preferably between 20 and 25 ° C.
  • the treatment of the heavy metal and phosphorus-containing solids by percolation of acid leaching liquid containing leachable, aerobic sulfur-oxidizing and anaerobically conditioned polyphosphate-storing microorganisms, carried by the medium to be treated can take place, for example, as heap leaching or heap leaching or as rent percolation (wet leasing).
  • the solid to be leached is in a percolator through which acid leaching liquor containing the leaching active, aerobic sulfur oxidizing and anaerobically conditioned polyphosphate storage microorganisms is percolated.
  • the leaching liquid is located in a reservoir, suitably a stirred reactor.
  • the percolated leach liquor is returned to the percolator, preferably via the reservoir.
  • the leaching rate is improved.
  • the continuous circulation of the circuit also ensures an optimum solution ratio for the heavy metals and the phosphorus as well as a continuous supply of microorganisms.
  • the resulting phosphate-enriched biomass is separated from the leaching solution, for example by centrifugation or filtration. Separated microorganisms can be continuously replaced by fresh microorganisms.
  • the separation of the phosphorus-enriched biomass occurs when the phosphate concentration in the leaching liquid has reached a minimum.
  • the leaching liquid enriched with heavy metals and / or the solid materials depleted in heavy metals can be separated off and isolated and sent for recycling.
  • the accumulated phosphorus is plant available and free of unwanted heavy metals.
  • the biomass obtained can be used as a plant-available nutrient source, for example as a biofertilizer, or for soil improvement.
  • the process described above thus allows a bioleaching of metal-containing and phosphorus-rich solids and the simultaneous selective extraction of phosphorus.
  • the process of the invention is therefore an inexpensive and environmentally friendly recycling method for the nutrient phosphorus.
  • the process is ideally suited for the decontamination of pollutant-containing solids that are depleted by heavy metals, and thus for soil remediation.
  • the solids depleted in heavy metal can be recycled without any problems, for example as building materials, in particular in road construction, since the limits of heavy metal pollution required for such uses are not exceeded.
  • the process of the present invention can also be used for the simultaneous efficient mobilization and recovery of heavy metals from the treated solid materials by concentrating the heavy metals contained in the resulting leach solution, for example via membrane equipment.
  • the starting material was anaerobically conditioned sewage sludge (digested sludge, solids content approx. 6%), which was obtained from an urban sewage treatment plant. As a result of a certain residence time in a digester this contains Digested sludge anaerobically conditioned polyphosphate-storing microorganisms with empty phosphate stores. The samples were collected in 21 polypropylene bottles and stored at 4 ° C until use.
  • Leaching active, aerobic sulfur oxidizing microorganisms were enriched in the digested sludge with the addition of elemental sulfur as an energy source and supply of CO 2 as a carbon source.
  • 2 l of anaerobically conditioned sewage sludge were mixed with 10 g / l of elemental sulfur in a 21-stirred reactor (1) with stirring (250 rpm) and aeration with compressed air containing oxygen and carbon dioxide. Enrichment took place at room temperature (25 ° C) without the addition of other nutrients.
  • the pH was measured daily. After reaching a pH of 2.3 to 2.4 (after about 22 days), the batch was centrifuged at 25,000 g for 20 min.
  • AEDS The supernatant (about 800 ml, hereinafter referred to as AEDS) enriched with leaching-induced, aerobic sulfur-oxidizing microorganisms and still containing polyphosphate-storing microorganisms was transferred to a second stirred reactor (2) and used as the leaching solution. The residue was discarded.
  • the stirred reactor (2) is connected to a percolator (3) with glass frit (4), whereupon the solid to be leached is.
  • a percolator (3) with glass frit (4), whereupon the solid to be leached is.
  • 2 grams of sewage sludge ash was used.
  • FIG. 2 is the content of some heavy metals in solution based on the total content of heavy metals in sewage sludge ash shown. Accordingly, between 40% (copper) and 70% (zinc) of the heavy metals contained in sewage sludge ash went into solution.
  • the phosphorus content of the AEDS was determined by ion chromatography and photometric measurements.
  • the dissolved phosphate or the accumulation of phosphate by the phosphate-accumulating bacteria contained in AEDS over time is in FIG. 3 represented (circles).
  • FIG. 3 represents (circles).
  • a marked clouding of the AEDS was observed, which was caused by the growth of the phosphate-accumulating bacteria present in the leaching solution. This was also the time when the bioaccumulation of phosphorus released by bioleaching significantly increased.
  • FIG. 3 from 300 mg / l on day 3 to approximately 0 mg / ml on day 11.
  • a pure Acidithiobacillus culture was used in a specially optimized nutrient medium in which no phosphate-accumulating bacteria were contained, the phosphorus accumulation from the solution remained largely ( FIG. 3 , Squares).
  • the phosphate-rich biomass was separated by centrifugation from the still-dissolved heavy metals, when the phosphorus content in the solution had reached a minimum value.
  • the inventive method thus allows efficient Biolaugung of metal-containing and phosphorus-rich solids with simultaneous selective recovery of phosphorus.
  • the mobilized heavy metals can also be recovered from the treated solids.

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EP20090781863 2008-08-15 2009-08-14 Verfahren zur Phosphorgewinnung aus Feststoffen unter Verwendung laugungsaktiver und phosphatakkumulierender Mikroorganismen Not-in-force EP2324118B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200810038886 DE102008038886A1 (de) 2008-08-15 2008-08-15 Beschrieben wird ein Verfahren zur selektiven Gewinnung von Phosphor aus schwermetall- undphosphathaltigen Feststoffen, bei dem die schwermetall- und phosphorhaltigen Feststoffe unter sauren aeroben Bedingungen mit Mikroorganismen behandelt werden, die laugungsaktive und polyphosphatspeichernde Mikroorganismen umfassen. Dabeiwerden Schwermetalle und Phosphat aus dem Feststoff freigesetzt und das freigesetzte Phosphat wird durch die polyphosphatspeichernden Mikroorganismen aufgenommen. Die mit Phosphor angereicherte Biomasse wird abgetrennt.
PCT/EP2009/060562 WO2010018228A2 (de) 2008-08-15 2009-08-14 Verfahren zur selektiven phosphorgewinnung aus feststoffen

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EP2324118A2 EP2324118A2 (de) 2011-05-25
EP2324118B1 true EP2324118B1 (de) 2012-02-01

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EP20090781863 Not-in-force EP2324118B1 (de) 2008-08-15 2009-08-14 Verfahren zur Phosphorgewinnung aus Feststoffen unter Verwendung laugungsaktiver und phosphatakkumulierender Mikroorganismen

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AT (1) ATE543908T1 (ja)
AU (1) AU2009281133B2 (ja)
CA (1) CA2734105A1 (ja)
CL (1) CL2011000320A1 (ja)
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MA (1) MA32636B1 (ja)
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DE102013226042A1 (de) 2013-12-16 2015-06-18 Helmholtz-Zentrum Dresden - Rossendorf E.V. Vorrichtung und Verfahren zur Gewinnung von 2- und 3-wertigen Metallionen aus primären und sekundären Rohstoffen mit Hilfe von mikrobiellen Metaboliten

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ES2623897T3 (es) 2014-03-10 2017-07-12 Udo Pauly Procedimiento para la separación de materias sólidas y recuperación de fosfatos a partir de suspensiones acuosas
DE102015107749A1 (de) * 2015-05-18 2016-11-24 Hannelore Markgraf Verfahren und Vorrichtung zur Anreicherung von Phosphor aus Klärschlamm
JP6941830B2 (ja) * 2016-03-10 2021-09-29 Ｊｆｅスチール株式会社 嫌気性膜分離活性汚泥装置
CN106631286B (zh) * 2017-01-16 2020-11-06 东北农业大学 一种通过生物聚磷制备的富磷高效堆肥产品及其方法
CN109264948A (zh) * 2018-09-24 2019-01-25 东北石油大学 油泥无害化处理装置以及方法
CN109762774A (zh) * 2019-03-12 2019-05-17 广州中大环境治理工程有限公司 一株高效除磷的不动杆菌根瘤菌及其应用
CN112777888B (zh) * 2020-12-24 2022-04-19 南京农业大学 一种基于生物硫循环实现废水污泥中重金属去除与回收的处理方法
CN112893443B (zh) * 2021-01-21 2022-03-22 郭云征 一种降低植物中重金属残留的方法
CN115889422A (zh) * 2021-09-29 2023-04-04 中国石油化工股份有限公司 处理含重金属固废的方法
CN115072875B (zh) * 2022-07-14 2023-10-10 华辰环保能源(广州)有限责任公司 一种线路板废水的好氧生物处理方法

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Publication number Priority date Publication date Assignee Title
DE102013226042A1 (de) 2013-12-16 2015-06-18 Helmholtz-Zentrum Dresden - Rossendorf E.V. Vorrichtung und Verfahren zur Gewinnung von 2- und 3-wertigen Metallionen aus primären und sekundären Rohstoffen mit Hilfe von mikrobiellen Metaboliten

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CN102124116A (zh) 2011-07-13
US20120103037A1 (en) 2012-05-03
MA32636B1 (fr) 2011-09-01
WO2010018228A3 (de) 2010-07-29
JP5746029B2 (ja) 2015-07-08
AU2009281133B2 (en) 2014-06-26
DE102008038886A8 (de) 2010-11-11
US9005956B2 (en) 2015-04-14
CA2734105A1 (en) 2010-02-18
WO2010018228A2 (de) 2010-02-18
DE102008038886A1 (de) 2010-03-04
RU2011103054A (ru) 2012-09-20
ATE543908T1 (de) 2012-02-15
CL2011000320A1 (es) 2011-08-26
JP2012500002A (ja) 2012-01-05
EP2324118A2 (de) 2011-05-25
AU2009281133A1 (en) 2010-02-18

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